Malononitrile → (1-Hydroxy-2-methylpropylidene)methane-1,1-dicarbonitrile

A solution of malononitrile (4.0 g, 60 mmol) in THF (30 mL) was added dropwise over 1 h to a suspension of NaH (95%, 3.0 g, 120 mmol) in THF (75 mL) at 0° C. The reaction was then warmed to room temp and stirred for 1 h. The suspension was then cooled to 0° C. and treated dropwise with a solution of isobutyryl chloride (6.3 mL, 60 mmol) in THF (25 mL). The addition was controlled so that the internal temp does not rise above 10° C. Upon completion of the addition the reaction was warmed to room temp and stirred for 24 h. The reaction was then quenched with H2O (10 mL) and evaporated. The residue was then partitioned between EtOAc (100 mL) and 1 N HCl (75 mL). The aqueous layer was extracted again with EtOAc (50 μL) and the combined organic layers were washed with brine (100 mL), dried (c), filtered, and evaporated to yield the desired product (7.95 g, 96%).

1. temperatureThe suspension was then cooled to 0° C.
2. additionThe addition
3. customdoes not rise above 10° C
4. additionUpon completion of the addition the reaction
5. temperaturewas warmed to room temp
6. stirringstirred for 24 h
7. customThe reaction was then quenched with H2O (10 mL)
8. customevaporated
9. customThe residue was then partitioned between EtOAc (100 mL) and 1 N HCl (75 mL)
10. extractionThe aqueous layer was extracted again with EtOAc (50 μL)
11. washthe combined organic layers were washed with brine (100 mL)
12. dry with materialdried (c)
13. filtrationfiltered
14. customevaporated

ORD-Eintrag

ord-97cce72102764eb0ad60a2bf1bd1e4b4

Quelldatensatz

uspto-grants-2009_10

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US07605175B2